Energetic azide plasticizer

ABSTRACT

Novel multi-azido formals, acetals and ketals are disclosed, having the following generic formula  &lt;IMAGE&gt;  in which R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from H, CH3, and CH2N3, and methods of preparation of these compounds.

This is a Division of application Ser. No. 07/320,142 filed Mar. 17, 1989, now U.S. Pat. No. 5,220,039.

BACKGROUND AND SUMMARY OF THE INVENTION

This invention relates to novel chemical compounds used as plasticizers in polymeric formulations. In particular, this invention relates to novel, energetic, methylazide-substituted formals, acetals and ketals. These compounds have utility as energetic plasticizers for rocket and gun propellant and explosive formulations. A process for their preparation is also presented, as well as energetic compositions which include the novel plasticizers.

Solid propellants, such as those used for rocket propellants, are prepared by combining a variety of materials consisting of oxidizers, binders, plasticizers and a curing agent to solidify the formulation. The plasticizers may be either energetic or non-energetic in nature. Energetic plasticizers tend to be somewhat viscous in nature, and this limits the amount of solids that can be included in propellant formulations while maintaining good propellant processibility. Reducing the solids loading of a propellant generally results in a lowered propellant impulse.

This invention relates to a novel class of methylazide substituted acetals, formals and ketals for use as plasticizers in propellant systems, many of which are capable of being prepared from readily available starting materials, and to a novel process for their preparation.

This invention also resides in energetic compositions which include the methylazide-substituted acetals, formals and ketals as plasticizers. Such compositions have the combined benefits of improved propellant performance due to the energetic nature of the plasticizer, high solids loading and ease of processibility of the propellant formulation. The term "energetic compositions" is intended to include rocket and gun propellant and explosive formulations.

DETAILED DESCRIPTION OF THE INVENTION

The novel methylazide-substituted acetal, formal and ketal compounds of the present invention are represented by the formula: ##STR2## wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are independently selected from the group consisting of H, CH₃, and CH₂ N₃, such that the total number of azide (N₃) groups is at least one. The term "independently selected" is used herein to indicate that two or more of the R groups may be identical.

Examples of acetals within the above formula are those in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are as follows:

    __________________________________________________________________________     R.sup.1                                                                            R.sup.2                                                                             R.sup.3                                                                            R.sup.4                                                                             R.sup.5                                                                            R.sup.6                                                                             R.sup.7                                                                            R.sup.8                                         __________________________________________________________________________     H   H    H   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                H   H    H   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                H   CH.sub.3                                                                            H   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                H   CH.sub.3                                                                            H   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                H   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                H   CH.sub.2 N.sub.3                                                                    H   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                H   CH.sub.3                                                                            H   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                H   CH.sub.3                                                                            H   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                H   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub. 3                                                                   CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                H   CH.sub.2 N.sub.3                                                                    H   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                CH.sub.3                                                                           H    CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.3                                                                           H    CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            CH.sub. 3                                                                          CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   H    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   H    CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    H   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.3                                                                           CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 N.sub.3                                                                    CH.sub.2 N.sub.3                                                                   CH.sub.2 N.sub.3                                __________________________________________________________________________

Within the scope of the above formula, certain embodiments are preferred, namely those in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently H or CH₂ N₃ ; those in which the total number of azide groups is at least two, preferably at least three, and most preferably at least four; those in which R⁶ and R⁸ are each CH₂ N₃ ; those in which R² and R⁷ are each CH₂ N₃ ; those in which R⁴, R⁵, R⁶, and R⁸ are each CH₂ N₃ ; and those in which R¹, R², R³, R⁶, R⁷, and R⁸ are each CH₂ N₃.

The compounds of the invention may be symmetrical or asymmetric. Symmetrical compounds are preferred, i.e., those in which R¹ and R³ are identical, R⁴ and R⁵ are identical, and R⁶ and R⁸ are identical.

The symmetrical compounds may be prepared by reacting a substituted alcohol with an aldehyde or ketone (or suitable oligomers such as trioxane) to form either a formal, an acetal or a ketal. The aldehyde or the ketone may or may not be substituted. The substitutions on the alcohol, aldehyde or ketone may consist of an azide group or any functional group that can be replaced by an azide group. Examples of the latter are halides such as chloride. In a typical reaction scheme, a halogen-substituted aliphatic alcohol is first reacted with a compound having an aldehyde or ketone functionality in the presence of a catalyst. This forms a formal (if formaldehyde is used), an acetal (if acetaldehyde is used) or a ketal (if a ketone is used), which is then reacted with a metal azide in a solvent to give the corresponding azide plasticizers. Examples of compounds having aldehyde or ketone functionalities are 1,3,5-trioxane, acetaldehyde, chloroacetaldehyde, acetone, and 1,3-dichloroacetone. Reactions of the alcohols with these compounds preferably take place at -5° C. to 35° C., in the presence of a catalyst, and are capable of producing yields above 95%. In preferred embodiments, however, the reactions are conducted at 15° C. to 25° C., with yields ranging from 75% to 85%. The reaction between the formal, acetal or ketal and the metal azide is preferably performed at 70° C. to 120° C., with yields ranging from 50% to 99%. Particularly preferred reactions are those involving the use of sodium azide at 75° C. to 100° C. with dimethyl sulfoxide as the solvent, whereupon yields of 95% to 99.9% may be obtained.

The asymmetrical compounds may be prepared by using a combination of alcohols rather than a single alcohol, then isolating the desired species from the product mixture using conventional purification techniques well known to those skilled in the art. Alternatively, the product mixture may itself be used without isolating single species.

The following example is intended to illustrate the invention and is in no way to be considered as a limitation on the inventive concept.

EXAMPLE

1. Preparation of bis(1,3-dichloro-2-propyl) Formal

A three-neck 500-mL flask equipped with a thermometer, a mechanical stirrer, an addition funnel, a condenser, and a positive nitrogen atmosphere were charged with 1,3-dichloro-2-propanol (51.6 g, 0.4 mole), trioxane (6.0 g, 0.2 mole as formaldehyde), and 1,2-dichloroethane (200 mL). The mixture was a clear yellow solution. Concentrated sulfuric acid (29.8 g, 0.29 mole) was then added dropwise over sixteen minutes. During the addition, a slight exotherm was observed, and the flask was immersed in a water bath to maintain the reaction temperature at 16°-25° C. Once the addition was complete, the water bath was removed and the reaction mixture was stirred at 18°-22.5° C. for 2.7 hours. The agitator was then turned off. The lower (acid) layer (weighing 28.62 g) was removed, washed once with 50 mL 1,2-dichloroethane, and discarded. The 1,2-dichloroethane layers were then combined and washed with two 300-mL portions of 1% aqueous NaHCO₃, followed by two 300-mL portions of deionized water. The solution was then stripped in vacuo leaving a yellow liquid, weighing 43.32 g (80.2% yield) which solidified into a slush-like consistency upon standing at ambient temperature. The product was identified as bis(1,3-dichloro-2-propyl) formal by proton nuclear magnetic resonance (NMR) (CDCl₃) δ4.8 (s, --OCH₂ O--), 4.0 (m, (ClCH₂)₂ CHO--), 3.6 (d, (ClCH₂)₂ CHO--).

2. Preparation of bis(1,3-diazido-2-propyl) Formal (BDPF)

A three-neck 250-mL flask equipped with a mechanical stirrer thermometer, addition funnel, heating mantle and nitrogen atmosphere was charged with dimethyl sulfoxide (75 mL) and heated to 75° C. Sodium azide (5.05 g, 77.7 mmoles) was then added in one portion. The mixture was heated to 95° C. The product of part 1 above (5.0 g, 18.5 mmoles) dissolved in 25 mL of dimethylsulfoxide was then added dropwise over thirty-two minutes at 94.5°-99.2° C. Upon completion of the addition, stirring was continued for four hours at 95°-99° C. The mixture was then cooled to ambient temperature, quenched with 200 mL of deionized water, and extracted with two 100-mL portions of methylene chloride. The resulting aqueous solution was discarded, and the combined methylene chloride phases were washed with two 200-mL portions of water and stripped in vacuo to give a yellow oil, weighing 5.42 g (98.7% yield). The oil was identified as bis(1,3-diazido-2-propyl) formal by infrared analysis (film): 2950 cm⁻¹ (CH), 2125 cm⁻¹ (N₃), 1290 cm⁻¹, 1175 cm⁻¹, 1120 cm⁻¹, 1040 cm⁻¹ (OCH₂ O); and proton NMR (CDCl₃) δ4.8 (s, OCH₂ O), 3.8 (m, (N₃ CH₂)₂ CHO), 3.3 (d, (N₃ CH₂)₂ CHO).

Table 1 presents physical properties and analytical results of neat BDPF, Table 2 presents calculated thermodynamic properties, and Table 3 hazard properties of BDPF neat and in solvent solutions. In the hazard properties tests, neat BDPF and BDPF solvent solutions were subjected to a series of standard tests using industry-accepted test procedures. These included Bureau of Mines Impact tests, electric spark sensitivity tests, rotary friction tests, differential thermal analyses (DTA), differential scanning calorimetry (DSC), Naval Ordnance Laboratory (NOL) etonability (card gap) tests and unconfined burning tests.

                  TABLE 1                                                          ______________________________________                                         PHYSICAL PROPERTIES and ANALYTICAL RESULTS,                                    NEAT BDPF                                                                      ______________________________________                                         Chemical structure: (N.sub.3 CH.sub.2).sub.2 CHOCH.sub.2 OCH (CH.sub.2         N.sub.3).sub.2                                                                 Molecular Formula: C.sub.7 H.sub.12 N.sub.12 O.sub.2                           Molecular Weight: 296.25                                                       Appearance: Colorless liquid                                                   Density: (@ 21° C.): 1.29 gm/ml                                         Freezing Point: -22° C.                                                 Purity (GC area %):                                                            Methylene Chloride      0.02                                                   Unknown Low Boilers     1.19                                                   Bis(1,3-dichloro-2-propyl) formal (BDCPF)                                                              0.55                                                   BDPF                    86.03                                                  Polyoxymethylene Derivatives of BDPF                                                                   12.21                                                  Totall Chloride (wt. %):                                                                               0.24                                                   Vacuum Stability (100° C., 48 hrs.), ml/gm:                                                     2.56;                                                                          2.58;                                                                          2.85                                                   ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                         THERMODYNAMIC PROPERTIES (calculated)                                          ______________________________________                                         Heat of formation, (kcal/mole)                                                                       +239.4                                                   Heat of combustion, (kcal/mole)                                                                     -1307.9                                                   ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                         HAZARD PROPERTIES OF BDPF SOLVENT                                              SOLUTIONS                                                                                  BDPF Concentrations                                                solvent:      CH.sub.2 Cl.sub.2  DMSO                                          Test    % BDPF:   100     50    40   20    30                                  ______________________________________                                         Impact (cm at 2 kg)                                                                          42-46   >100    --   >100  >100                                  Spark sensitivity                                                                            >1.0    >1.0    --   >1.0  >1.0                                  (joules)                                                                       Rotary friction                                                                              1000-   >4000   --   >4000 >4000                                 (g at 2000 rpm)                                                                              1060                                                             DTA (°C.)                                                               exotherm onset                                                                               159     169     --   198   150                                   exotherm peak 218     206     --   219   185,                                                                           188                                   DSC (°C.)                                                               exotherm onset                                                                               218     --      --   --    --                                    exotherm peak 247     --      --   --    --                                    NOL card gap using                                                                           --      pos     neg  --    --                                    zero cards                                                                     Unconfined burn of                                                                           --      --      --   --    576                                   100 mL sample (sec)                                                            ______________________________________                                    

To those skilled in the art, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that the present invention may be practiced otherwise than as specifically described herein and still be within the spirit and scope of the appended claims. 

What is claimed is:
 1. A method for preparing a compound having the formula ##STR3## in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selected from the group consisting of H, CH₃, and CH₂ N₃ such that the total number of azide groups is at least one, said method comprising:(a) reacting a halogen-substituted alcohol in the presence of a catalyst with a compound having a functionality selected from aldehyde and ketone functionalities; and (b) reacting the product of step (a) with metal azide to obtain said compound.
 2. A method in accordance with claim 1 in which the total number of azide groups is at least two.
 3. A method in accordance with claim 1 in which the total number of azide groups is at least three.
 4. A method in accordance with claim 1 in which the total number of azide groups is at least four.
 5. A method in accordance with claim 1 in which the total number of azide groups is three.
 6. A method in accordance with claim 1 in which the total number of azide groups is four.
 7. A method in accordance with claim 1 in which the total number of azide groups is five.
 8. A method in accordance with claim 1 in which the total number of azide groups is six.
 9. A method in accordance with claim 1 in which the total number of azide groups is seven.
 10. A method in accordance with claim 1 in which the total number of azide groups is eight.
 11. A method in accordance with claim 1 in which R¹ and R³ are identical, R⁴ and R⁵ are identical, and R⁶ and R⁸ are identical.
 12. A method in accordance with claim 1 in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selected from the group consisting of H and CH₂ N₃.
 13. A method in accordance with claim 1 in which R⁶ and R⁸ are each CH₂ N₃.
 14. A method in accordance with claim 1 in which R² and R⁷ are each CH₂ N₃.
 15. A method in accordance with claim 1 in which R⁴, R⁵, R⁶ and R⁸ are each CH₂ N₃.
 16. A method in accordance with claim 1 in which R⁴, R⁵, R⁶, and R⁸ are each CH₂ N₃ ; R¹, R², and R³ are each H; and R⁷ is CH₃.
 17. A method in accordance with claim 1 in which R¹, R², R³, R⁶, R⁷, and R⁸ are each CH₂ N₃.
 18. A method in accordance with claim 1 in which R⁴, R⁵, R⁶, and R⁸ are each CH₂ N₃, and R¹, R², R³ and R⁷ are each H. 